Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
  • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
  • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
  • C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
  • D06M2200/11—Oleophobic properties
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
  • D06M2200/12—Hydrophobic properties

Definitions

• Liquid repellent composition liquid repellent processing method, article having liquid repellent film
• the present invention relates to a liquid repellent composition, a liquid repellent processing method, and an article having a liquid repellent film.
• a structural unit of a polymerizable monomer containing a polyfluoroalkyl group (hereinafter, a polyfluoroalkyl group is referred to as an Rf group) in the molecule.
• An article using an organic solvent solution or an aqueous dispersion of a copolymer containing the above or a copolymer of this and other monomers (hereinafter also referred to as R f group-containing polymer). Processing has been done.
• a composition comprising a copolymer containing a structural unit of a crystalline Rf group-containing monomer (hereinafter, also referred to as a crystalline polymer) as an active ingredient is from the viewpoint of developing water and oil repellency.
• a copolymer containing a structural unit of a crystalline Rf group-containing monomer hereinafter, also referred to as a crystalline polymer
• ability to achieve objectives Other practical functions have been improved. For example, in order to improve durability against washing, dry cleaning, friction, etc., a monomer having high hardness or a monomer having a cross-linking reactive group is used together with the crystalline Rf group-containing monomer. Improvements have been made.
• cosmetic compositions containing a fluorine-based compound and a wax having a specific melting point see, for example, Patent Document 1
• group (meth) acrylate and stearyl (meth) acrylate and two other types 4 terpolymer of the monomer as an essential component e.g., see Patent Document 2;.
• fluorine-containing water- and oil-repellent and a specific chain length of R F group-containing alcohol or Pafuruoropori alcohols containing ether groups of the formulation for example, see Patent Document 3
• a reaction product of an amino group-containing silicone and an Rf group-containing ester compound see, for example, Patent Document 4
• an example of limiting the chain length of the R f group-containing monomer to be used is an acrylic seven-component copolymer (see, for example, Patent Document 5) that defines the chain length distribution of R F groups. At least 40% of a monomer containing a crystalline R f group.
• Techniques in this field, represented by these known examples, have improved surface properties and physical properties required for functions other than impairing the water and oil repellency inherent to the R f group.
• the crystalline polymer containing the R f group is the main component, the drawbacks described later have not been able to be fundamentally improved.
• Patent Document 1 Japanese Patent Laid-Open No. 7-173025
• Patent Document 2 Japanese Patent Laid-Open No. 10-237133
• Patent Document 3 Japanese Patent Laid-Open No. 10-81873
• Patent Document 4 JP-A-8-109580
• Patent Document 5 JP-A 62-179517
• Crystalline R f group-containing monomer and chloride The force used to improve the adhesion by using a copolymer with a specific monomer such as Bulle. This method tends to harden the texture of the fiber, so the adhesion and texture! , Cann't be compatible!
• a medium for water and oil repellents a medium mainly composed of water (hereinafter referred to as an aqueous medium), an alcohol solvent, a petroleum solvent called a weak solvent, or a hyde mouth fluorocarbon is used.
• an aqueous medium a medium mainly composed of water
• an alcohol solvent a solvent mainly composed of water
• a weak solvent a solvent mainly composed of water
• An object of the present invention is to provide a liquid repellent composition capable of imparting excellent liquid repellency and durability to a substrate, and an article having a liquid repellent film using the liquid repellent composition.
• the present invention is a liquid repellent composition containing a copolymer (I) and a copolymer (II), wherein the copolymer (I) has a mass ratio with respect to the copolymer (I), It contains 65 to 95% by mass of the structural unit (a) and 1 to 30% by mass of the structural unit (b), and the copolymer ( ⁇ ) has a mass ratio of 25 to 25% relative to the copolymer (II).
• copolymer (I) containing 80% by mass of the structural unit (a) and 1-50% by mass of the structural unit (c) and contained in the copolymer (I)
• mass ratio to the copolymer (II) of the structural unit (a) contained in the copolymer ( ⁇ ) is [a]
• mass ratio to the copolymer (II) is [a] — [a] ⁇ 10 (mass%)
• the structural unit (a) is a structural unit derived from a monomer represented by (Z — Y) X.
• Z is a polyfluoroalkyl group having 6 or less carbon atoms.
• n is 1 or 2
• HCOO ⁇ (R is a hydrogen atom, methyl group or halogen atom. ⁇ is a phenylene group. M is an integer of 0 to 4.) Y is a divalent organic group or a single bond.
• the structural unit (b) is a structural unit derived from a monomer represented by Z—X.
• X is the same as X above.
• the structural unit (C) is a structural unit derived from a monomer having no polyfluoroalkyl group and having a crosslinkable functional group.
• the liquid repellent composition of the present invention is characterized in that the copolymers (I) and Z or the copolymer ( ⁇ ) have a polymerizable property other than the structural units (a), (b) and (c). It is preferable to contain the structural unit (d) derived from a monomer having a group.
• the liquid repellent composition of the present invention preferably further contains a surfactant (III).
• the surfactant (III) comprises the following surfactant (el) and Z or surfactant (e2), and surfactant (e3).
• the surfactant (el) is at least one selected from the group consisting of polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkyl polyether and polyoxyalkylene monopolyfluoroalkyl ether. is there.
• Surfactant (e2) is a nonionic surfactant comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.
• Surfactant (e3) is a cationic surfactant represented by the following formula s 71.
• R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a terminal hydroxyl group. There, the four R 21 may be the same or different, four R 21 are not hydrogen atom at the same time. Shows strawberry counter ion.
• liquid repellent processing method using the liquid repellent composition and an article having a liquid repellent film formed using the liquid repellent composition.
• the invention's effect it is possible to provide a liquid repellent composition that can impart water repellency with excellent durability to an article.
• the liquid repellent composition of the present invention can be used to provide an article having excellent liquid repellency and high durability V repellent film.
• FIG. 1 is a graph showing the thermogravimetric loss (TG-DTA) of each additive.
• FIG. 2 is a diagram showing changes in dynamic surface tension.
• the liquid repellent composition of the present invention contains a copolymer (I) and a copolymer ( ⁇ ), and the copolymer (I) and the copolymer ( ⁇ ) are structural units (a) -(D) can be contained.
• the copolymer (I) contains the structural unit (a) and the structural unit (b)
• the copolymer (II) contains the structural unit (a) and the structural unit (c).
• Copolymer (I) mainly contributes to the expression of liquid repellency of the liquid repellent composition
• copolymer ( ⁇ ) mainly contributes to the durability of the liquid repellent composition.
• the structural unit (a) is a monomer having an R f group represented by (Z — Y) X
• Z is an R f group with 6 or fewer carbon atoms, and n is 1 or less.
• OCH CHCOO- (R is a hydrogen atom, a methyl group or a halogen atom. ⁇ is a phenylene group. M is an integer of 0-4). Y is a divalent organic group or a single bond.
• the structural unit (a) of the present invention may be derived from a mixture of two or more monomers having the above R f group.
• the structural unit (a) mainly contributes to the development of water repellency of the liquid repellent composition.
• the R f group is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and has 1 to 6 carbon atoms. However, when the R f group has ether-based oxygen, the number of carbon atoms may be 1-20.
• the R f group is preferably a group in which at least 20 to 80% of hydrogen atoms of the alkyl group are substituted with fluorine atoms. Further, some or all of the remaining hydrogen atoms may be substituted with chlorine atoms.
• the R f group may be linear or branched. In the case of branching, the bond strength is also short at or near the far end. Those having a branch are preferred. Further, among the above preferred R f groups, F (CF) (h
• 2 h is a linear R F group represented by: CF (CM'M'CM'M 4 ) (M ⁇
• M 2 , M 3 and M 4 are each independently a hydrogen atom, a fluorine atom or a chlorine atom, and one of them is a fluorine atom. ) Is more preferable. Those having a small number of carbon atoms are preferable because, when a homopolymer is formed, microcrystals derived from the R f group hardly appear, and the copolymer can form a flexible film.
• the R f group may be a chain polyfluorohydrocarbon group having one or more unsaturated groups such as a carbon-carbon unsaturated double bond.
• R F groups include, but are not limited to, the following R F groups:
• examples of the R F group containing ether-based oxygen include CF 0 [CF (CF) CF k 2k + l 3 2
• the R f group and the polymerizable unsaturated group may be bonded by a single bond or may be bonded via a divalent organic group.
• the divalent organic group is preferably a group containing an alkylene group.
• the alkylene group may be linear or branched.
• the divalent organic group includes O, 1 NH, 1 CO—, and —SO D 2.
• Etc. may be included.
• the divalent organic group an alkylene group is preferable.
• Y is -CH-, one CH C
• X represents an ethylenically polymerizable unsaturated group, that is, a residue of olefins, vinyl
• Residues of ruethers, residues of butyl esters, residues of (meth) acrylates, residues of maleates, residues of fumarates are preferred.
• a group represented by — is shown.
• R is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, etc.) or a short chain of 1 to 3 carbon atoms in order not to disturb the polymerizability Of these, an alkyl group (particularly a methyl group) is preferred.
• X is (meta
• Residues of acrylates, maleic acid or fumaric acid esters are preferred in terms of solubility in a solvent or ease of emulsion polymerization, etc. Metatalylate residues are preferred.
• the R f monomer is particularly preferably a (meth) acrylate having an R f group, and particularly preferably a meta acrylate having an R f group.
• various monomers such as the following monomers can be used.
• known monomers can be used.
• Examples of the monomer forming the structural unit (a) used in the present invention include polymerizability with other monomers, flexibility of the formed film, adhesion to the substrate, solubility in the solvent, and ease of emulsion polymerization. From the viewpoint of properties, etc., (meth) acrylates are particularly preferred as mentioned above.
• R f group is R F group
• Y is — (CH 2) —, — (CH 2 CH 3) — or — (CH 2) —
• the R f group of the monomer of the structural unit (a) of the present invention is an R F group having 6 or less carbon atoms, and is preferably a linear R F group having 4 to 6 carbon atoms.
• the number of carbon atoms of the R f group is preferably 4 to 6.
• the structural unit (b) in the present invention is a structural unit derived from a monomer represented by Z —X. is there.
• Z is a hydrocarbon group having 14 or more carbon atoms, even if it is a saturated hydrocarbon group
• Unsaturated hydrocarbon group straight chain or branched, for example, tetradecyl group, cetyl group, heptadecyl group, stearyl group, icosyl group, behenyl group, laurone group , Tetracosyl group, montanyl group, stearone group.
• X is an ethylenically polymerizable unsaturated group, that is, a residue of olefins, vinyl ether
• Residues of vinyls, residues of vinyl esters, residues of (meth) acrylates, residues of maleic esters, residues of fumaric esters and the like are preferred.
• the residue of olefins—CR CH
• the residue of bulules—COOCR CH
• burether
• R is preferably a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, etc.) or a short-chain alkyl group having 1 to 3 carbon atoms (particularly a methyl group) in order not to disturb the polymerizability.
• X includes (meth) atarylates, bull ethers, bull es
• the monomer forming the structural unit (b) a mixture of two or more kinds may be used.
• the monomer forming the structural unit (b) is preferably a monomer having a saturated hydrocarbon group having 16 to 40 carbon atoms, and an alkyl group having 16 to 40 carbon atoms. It is more preferable to use stearyl (meth) acrylate and beher (meth) acrylate, which are more preferable to contain (meth) acrylate.
• the copolymer containing the structural unit (b) can impart excellent water and oil repellency to the fiber.
• the structural unit (c) in the present invention is a monomer derived from a monomer having no R f group and having a crosslinkable functional group.
• the functional group capable of crosslinking is preferably a force having at least one bond among a covalent bond, an ionic bond and a hydrogen bond, or a functional group capable of forming a crosslinked structure by the interaction of the bonds.
• the functional group include isocyanate groups, blocked isocyanate groups, alkoxysilyl groups, amino groups, alkoxymethylamide groups, silanol groups, ammonium groups, amide groups, epoxy groups, hydroxyl groups, oxazoline groups, and force oxyl groups.
• Group, alkenyl group, sulfonic acid group and the like are preferable.
• epoxy group, hydroxyl acid Group, blocked isocyanate group, alkoxysilyl group, amino group and carboxyl group are more preferred.
• Preferred examples of the monomer that forms the structural unit (c) include (meth) acrylates, compounds having two or more copolymerizable groups, butyl ethers, and butyl esters.
• the structural unit (c) may be derived from a mixture of two or more kinds.
• Preferred examples of the monomer forming the structural unit (c) include the following compounds.
• 2 Isocyanatoethyl (meth) atarylate, 3 Isocyanatopropyl (meth) atalylate, 4—Isocyanatobutyl (meth) atalylate, 2-Isocyanatoethyl (meth) atalylate 2-butanone oxime adduct, 2 —Isocyanatoethyl (meth) atarylate pyrazole adduct, 2 Isocyanatoethyl (meth) atarylate adduct of 3,5 dimethylvirazole, 2 Isocyanatoethyl (meth) atarylate 3-methylbiazole Adduct, ⁇ -force prolatatam adduct of 2-isosocyanatoethyl (meth) ate, 3-isocyanatopropyl (meth) atalylate with 2 butanoxime, 3-isocyanatopropyl (meth) ate Pyrazole adduct.
• t-butyl (meth) acrylamide sulfonic acid (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, darisidyl (meth) acrylate, 2-hydroxyl Cyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene glycol mono (meth) acrylate , (Meth) acrylic acid, 2- (meth) attaroylkischetil succinic acid, 2- (meth) attaroyloxyhexahydrophthalic acid, 2- (meth) attaroyloxychetyl acid phosphate, allyl (meth) ) Atarylate, 2—Buhl—2-Oxazoline, 2—Buy - 4-methyl - (2-bi - Ruokis
• T (M) AIC Tri (meth) allyl isocyanurate
• TAC triallyl cyanurate
• HAT-600 glycidylethyl allylate tolylene diisocyanate
• the structural unit (c) mainly affects the film-forming property of the liquid-repellent film and the adhesiveness and adhesion of the liquid-repellent composition to the base material, and contributes to enhancing the durability.
• the structural unit (d) in the present invention is a structural unit derived from a monomer having a polymerizable group other than the structural units (a), (b) and (c). Further, it is preferable that the film is derived from a monomer having good film-forming properties and capable of obtaining a uniform copolymer solution or dispersion. Examples of the monomer that forms the structural unit (d) include the following.
• Crotonic acid alkyl ester maleic acid alkyl ester, fumaric acid alkyl ester, citraconic acid alkyl ester, mesaconic acid alkyl ester, allylic acetate, N-butylcarbazole, maleimide, N-methylmaleimide, and silicone in the side chain (meth ) Acrylate, (meth) acrylate having a urethane bond, (meth) acrylate having a polyoxyalkylene chain whose terminal is an alkyl group having 1 to 4 carbon atoms, alkylene di (meth) acrylate, etc.
• the structural unit (d) in particular, vinyl chloride, vinylidene chloride, cyclohexyl methacrylate, polyoxyethylene di (meth) acrylate, polyoxyethylene di (meth) acrylate alkyl ether, dioctyl maleate It is preferable to derive from ate.
• the structural unit (d) can contribute to the improvement of the adhesion of the composition to the substrate and the improvement of the dispersibility.
• copolymer (I) and the copolymer ( ⁇ ) of the liquid repellent composition of the present invention have the configuration described above. Units (a) to (d) can be contained.
• the copolymer (I) of the liquid repellent composition of the present invention contains 65 to 95% by mass of the structural unit (a) based on the mass of the copolymer (I).
• the content of the structural unit (a) in the copolymer (I) is preferably 70 to 95% by mass, more preferably 70 to 90% by mass.
• the structural unit (a) contained in the copolymer (I) is within this range, the liquid repellency can be sufficiently exhibited.
• the copolymer ( ⁇ ) contains 25 to 80% by mass of the structural unit (a) based on the mass of the copolymer ( ⁇ ).
• the content of the structural unit (a) in the copolymer ( ⁇ ) is preferably 30 to 80% by mass, more preferably 30 to 75% by mass.
• the constituent unit ( ⁇ ) in the copolymer ( ⁇ ) is within this range, the liquid repellency can be kept high.
• the mass ratio of the structural unit (a) contained in the copolymer (I) to the copolymer (I) is [a]
• the copolymer of the structural unit (a) contained in the copolymer ( ⁇ ) is [a]
• the copolymer (I) contains 1 to 30% by mass of the structural unit (b).
• the constituent unit (b) in the copolymer (I) is preferably 1 to 27% by mass, more preferably 3 to 27% by mass. If the structural unit (b) in the copolymer (I) is within this range, the liquid repellency can be sufficiently exhibited.
• the copolymer ( ⁇ ) contains 1 to 50% by mass of the structural unit (c).
• the structural unit (c) in the copolymer ( ⁇ ) is preferably 1 to 40% by mass, more preferably 1 to 35% by mass. If the structural unit (c) in the copolymer ( ⁇ ) is within this range, the durability can be sufficiently exhibited.
• the form of copolymer (I) and copolymer ( ⁇ ) is a form in which copolymer (I) and copolymer ( ⁇ ) are randomly mixed as separate particles.
• the copolymer (I) and the copolymer ( ⁇ ) are present in the same particle (for example, core-shell type).
• the structural unit (a) is 20 to 95% by mass in the entire copolymer. It is more preferably 30 to 90% by mass.
• the structural unit (b) is preferably 0.1 to 80% by mass in the entire copolymer, more preferably 0.5 to 70% by mass.
• the structural unit (c) is preferably 0.1 to 20% by mass in the entire copolymer, more preferably 0.5 to 15% by mass.
• the constituent unit (d) is preferably from 0.1 to 30% by mass, more preferably from 1 to 20% by mass, based on the entire copolymer. When the composition is within this range, the resulting liquid repellent composition has superior liquid repellency and durability.
• the copolymer (II) is present in the fine particle dispersion of the copolymer (I).
• Copolymer particles having a form in which the copolymer (I) is present on the surface of the fine particles of the force copolymer (I) or the inside thereof are preferred.
• the core-shell type in which the copolymer (I) and the copolymer ( ⁇ ) are separated into layers, is preferable in terms of performance. It may be in a form in which a part thereof is localized or a form in which other copolymer molecular chains are entangled.
• excellent water and oil repellency which can hardly be obtained by the method of producing and mixing the dispersion of copolymer (I) and the dispersion of copolymer ( ⁇ )) ( It is estimated that (liquid repellency) is obtained.
• the core part is the copolymer (I) and the shell part is the copolymer ( It is preferable to use i).
• the function related to the adhesive adhesion of the copolymer ( ⁇ ) can be enhanced, and durability can be improved.
• an effective sea-island structure can be formed on the film, high liquid repellency can be obtained.
• the copolymer (I) of the present invention contains the structural unit (a) and the structural unit (b)! / If it contains, it contains the structural unit (c) and the structural unit (d)! / .
• the copolymer ( ⁇ ) of the present invention contains the structural unit (a) and the structural unit (c)! / If included, it contains the structural unit (b) and the structural unit (d). Also good.
• the copolymer (I) and the copolymer ( ⁇ ) of the present invention are of core-shell type, the copolymer (I) and the copolymer ( ⁇ ) both contain the structural unit (d). I like it.
• the copolymer (I) composed of the structural units (a) and (b) and the copolymer (a ) And () and () a combination of structural units (a) and (b) copolymer (I) with force and copolymers (a), (c) and (d)
• the structural unit (a), (b), (c) and (d) is contained in the particle
• the structural unit (a) is 55 to 95% by mass in the entire copolymer, more preferably 60 to 90% by mass.
• the constituent unit (b) is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 15% by mass, based on the entire copolymer.
• the structural unit (c) is preferably 0.1 to 20% by mass in the entire copolymer, more preferably 0.5 to 10% by mass.
• Constituent units (d) are in the copolymer, and more preferably preferably tool 1 to 20 mass 0/0 that is 0.1 to 30 weight 0/0. If the composition is within this range, the resulting liquid repellent composition has superior liquid repellency and durability.
• the structural unit (a) is preferably 55 to 95% by mass in the entire copolymer. More preferably, it is 60-90 mass%.
• the structural unit (b) is preferably from 0.1 to 30% by mass, and more preferably from 0.5 to 15% by mass in the entire copolymer.
• the structural unit (c) is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, based on the entire copolymer.
• the structural unit (d) in the copolymer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass. When the composition is within this range, the resulting liquid repellent composition has superior liquid repellency and durability.
• the method for preparing the copolymer (I) and the copolymer (II) as active ingredients is not particularly limited.
• non-ionic surfactant and Z or cationic surfactant, non-ionic surfactant and Z or amphoteric surfactant, non-ionic surfactant and Z or key in water as a dispersion medium
• Conventional polymerization reaction methods such as a dispersion polymerization method including an on-surfactant, an emulsion polymerization method, and a suspension polymerization method can be employed.
• the obtained copolymer solution, dispersion, and emulsion may be used as they are or may be used after dilution. Further, after the copolymer is separated, it may be dissolved, dispersed, or emulsified in a solvent, a dispersion medium, or an emulsion polymerization medium. [0042] It is preferable to pre-emulsify using a high-pressure emulsifier or the like before the start of the polymerization reaction. For example, it is preferable to mix and disperse a monomer, a surfactant and a mixture that also has an aqueous medium power with a homomixer or a high-pressure milking machine. It is preferable to preliminarily mix and disperse the polymerization mixture before the start of polymerization because the yield of the finally obtained copolymer is improved.
• the copolymer (I) and the copolymer ( ⁇ ) are mixed separately, the copolymer (I) and the copolymer ( ⁇ ) are separately polymerized to obtain a copolymer. It is preferable to prepare the dispersions of the polymer (I) and the copolymer (i) after mixing the dispersions.
• the copolymer (I) and the copolymer ( ⁇ ) are present in the same particle, a method of reacting a polymerizable monomer at a time may be used, or the copolymer (I) A method of polymerizing the monomer constituting the copolymer ( ⁇ ) in the presence thereof may also be used.
• the latter method is not particularly limited, but the monomers constituting the copolymer (II) can be added to the emulsion or dispersion in which the copolymer (I) is present as fine particles in one step or several steps.
• a method in which a polymerization initiator is added and then polymerized by adding a polymerization initiator is preferred.
• the copolymer (I) and the copolymer (II) are preferably dispersed as particles in a medium.
• the number average particle size of the copolymer dispersed in the medium is preferably 10 to 1000 nm, more preferably 10 to 300 nm, and particularly preferably 10 to 200 nm.
• the average particle size is within this range, water and oil repellency is good without the need to use a large amount of a surfactant, a dispersant, etc., and color fading does not occur when processed into dyed fabrics. It is preferable because the dispersed particles can exist stably in the medium and do not settle.
• the average particle diameter can be measured with a dynamic light scattering device, an electron microscope, or the like.
• the liquid repellent composition of the present invention preferably uses a medium.
• the medium include water, alcohol, glycol, glycol ether, halogen compound, hydrocarbon, ketone, ester.
• one or more media selected from the group consisting of water, alcohols, glycols, glycol ethers and glycol esters are soluble. Viewpoint of ease of handling is preferable. Preferred examples of the medium are given below.
• Examples of alcohols include methanol, ethanol, 1 propanol, 2 propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1 pentanol, 2 pentanol, 3 pentanol, 2— Methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol monool, 1,2-dimethylenopropanol, 1-hexanol, 2-methylolene 1-pentanol, 4-methyl- Preferred examples include 2 pentanol, 2 ethyl 1-butanol, 1 heptanol, 2 heptanol, 3 heptanol and the like.
• glycols and glycol ethers include ethylene glycol, ethylene glycol monomethylenoatenore, ethyleneglycolenomonoethylenotenole, ethyleneglycolenonobutinoreethenole, ethyleneglycolmonomethyletheracetate, ethylene Glycomonolenoethylenoateolate, ethyleneglycolenobutinolenoatenoate, propylene glycol, glycol ether include propylene glycol monomethyl ether, propylene glycol monoethanolate ether , Propylene glycol dimethylol ether, dipropylene glycol, dipropylene glycol monomethylol ether, dipropylene glycol dimethyl ether, dipropylene glycol monomer Echiruete Le, tripropylene glycol, tripropylene glycol monomethyl ether, Polypropylene glycol, hexylene glycol, and the like preferably to.
• halogen compound examples include halogenated hydrocarbons and halogenated ethers.
• halogenated hydrocarbons include hydrated chlorofluorocarbon, hydrogen, id fluorinated carbon, and hydrobromocarbon.
• Hyde mouth black mouth fluorocarbon is CH CC1 F, CHC1 CF CF, CHC1FC
• Preferred examples include F CC1F.
• Hydrobroke mouth mochabons include CH Br, CH BrCH CH, CH CHBrCH, C
• Preferred examples of the halogenated ether include a hyde mouth fluoroether
• examples of the hyde mouth fluoroether include a separated type hyde mouth fluoroether and a non-separable type hyde mouth fluoroether.
• the separated type, iodofluor ether is a compound in which a perfluoroalkyl group or a perfluoroalkylene group, and an alkyl group or an alkylene group are bonded via an etheric oxygen atom.
• the non-separated type of hyde mouth fluoroether is a hyde mouth fluoro ether containing a partially fluorinated alkyl group or alkylene group.
• Separable Hyde Mouth fluoroethers include CF CF CF OCH, (CF) CFOCH
• Preferred examples include F CF OCH CH and C H OCF (CF) CF OCH.
• Non-separable Hyde mouth fluoroethers include CHF OCF OCHF and CH FCF OC
• Preferred examples include CHF OCF OCF OCF OCHF and the like.
• hydrocarbon examples include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.
• Aliphatic hydrocarbons include pentane, 2-methylbutane, 3-methylpentane, hexane, 2, 2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2, 2, 4-trimethylpentane, 2 2,3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, hexadecene and the like are preferable.
• Preferred examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and the like.
• Preferred examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.
• ketones include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, and the like.
• ester examples include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, and pentyl lactate.
• Preferred examples of the ether include diisopropyl ether, dioxane, tetrahydrofuran and the like.
• nitrogen compound examples include pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
• Preferred examples of the sulfur compound include dimethyl sulfoxide and sulfolane.
• the inorganic solvent is preferably liquid diacid-carbon.
• organic acid examples include acetic acid, propionic acid, malic acid, and lactic acid.
• the medium may be used as a mixture of two or more kinds. In the case of mixing with water, it is preferable to use it.
• a mixed medium the solubility and dispersibility of the copolymer can be controlled by controlling the permeability to the substrate, wettability, solvent drying speed, etc. during the blocking process.
• the liquid repellent composition of the present invention preferably contains a surfactant ( ⁇ ) in order to facilitate dispersion of the copolymer in the medium.
• a surfactant for example, 4 parts or less.
• hydrocarbon-based or fluorine-based surfactants can be used, and ionic, non-ionic, cationic or amphoteric surfactants can be used.
• ionic, non-ionic, cationic or amphoteric surfactants can be used.
• a nonionic surfactant and a cationic surfactant in combination at a mass ratio of 97Z3 to 40Z60.
• the total amount used can be reduced to 5% by mass or less based on the polymer, so the hydrophilicity is reduced and the substrate is excellent. Water repellency can be imparted.
• non-ionic surfactant one or more nonionic surfactants selected from the following surfactants are also preferred.
• Surfactant s 1 polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkyl ether, or polyoxyalkylene monopolyfluoroalkyl ether.
• Surfactant s 2 A nonionic surfactant comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.
• Surfactant s 3 Okishiechiren and a ⁇ chain continuous consecutive two or more connected and a chain Okishiarukiren having 3 or more carbon atoms is continuous in succession two or more, and both ends hydroxyl
• Surfactant Nonionic surfactant having an amine oxide moiety in the molecule
• Surfactant s 5 Condensate of polyoxyethylene mono (substituted phenyl) ether or polyoxyethylene mono (substituted phenyl)
• Surfactant s b A nonionic surfactant such as a fatty acid ester of polyol.
• the alkyl group, alkenyl group, alkyl group or polyfluoroalkyl group (hereinafter referred to as R s group) in the surfactant s 1 preferably has 4 to 26 carbon atoms.
• the R s group may be linear or branched. As the branched structure, a secondary alkyl group, a secondary alkyl group or a secondary alkapolyol group is preferable. Also, some or all of the hydrogen atoms may be substituted with force S fluorine atoms!
• R s group examples include an octyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, hexadecyl group, behexyl group (docosyl group), and oleyl group (9-octadecyl group). ), Heptadecylfluorooctyl group, tridecylfluorohexyl group, 1H, 1H, 2H, 2H-tridecylfluorooctyl group, 1H, 1H, 2H, 2H nonafluorohexyl group, and the like.
• the surfactant s 1 is preferably polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether or polyoxyalkylene monopolyfluoroalkyl ether.
• R 1 may be used alone or in combination of two or more.
• the polyoxyalkylene (hereinafter referred to as POA) chain of surfactant s 1 is preferably a chain in which at least two polyoxyethylene (hereinafter referred to as POE) chains and Z or polyoxypropylene (hereinafter referred to as POP) chains are connected. .
• POE polyoxyethylene
• POP polyoxypropylene
• One POA chain may be used alone, or two or more POA chains may be used in combination. If there are two types of power, it is preferable that the chain is block-shaped.
• the surfactant s 1, a compound represented by the following formula S 11 is more preferable.
• R 1C> represents an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms, q represents 0 or an integer of 1 to 20, and r represents an integer of 5 to 50.
• R 1C) is preferably a linear or branched structure, q is 0 or an integer of 1 to 10, and r is an integer of 10 to 30.
• r is 4 or less or q is 21 or more, it becomes poorly soluble in water and does not dissolve uniformly in an aqueous medium, so that the effect of penetrating the liquid repellent composition into the object to be treated is reduced.
• r is 51 or more, the hydrophilicity increases and the water repellency decreases.
• the following compounds are specific examples of the compound represented by the formula s 11. However, the POE chain and the POP chain are linked in block form.
• Surfactant s 2, 1 carbon-carbon triple bond in the molecule, and Roh a one or a compound having two hydroxyl groups - are preferably on surfactant.
• Surfactant s 2 may have a POA chain in the molecule.
• Examples of the POA chain include a POE chain, a POP chain, a chain in which a POE chain and a POP chain are randomly linked, or a chain in which a POE chain and a POP chain are linked in a block shape.
• a compound represented by the following formula s 21 , the following formula s 22 , the following formula s 23 or the following formula s 24 is preferable.
• a ⁇ A 2 and A 3 each independently represent an alkylene group
• u and V each represent an integer of 0 or more
• (u + v) represents an integer of 1 or more
• w represents an integer of 1 or more.
• AA 2 and A 3 may be used alone or in combination of two or more.
• Rn R 16 each independently represents a hydrogen atom or an alkyl group.
• the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.
• the POA chain is preferably a POE chain, a POP chain, or a chain containing a POE chain and a POP chain.
• the number of repeating units of the POA chain is preferably 1-50.
• a nonionic surfactant represented by the following formula s 25 is preferable.
• X and y are each 0 or 1 to: an integer of L00.
• Bruno formula s 25 - O emissions surfactant may be used in combination either singly or in combination.
• Nonionic surfactants of the formula s include those having X and y of 0, the sum of X and y is 1 to 4 on average, or the sum of X and y is 10 to 30 on average.
• An on-active surfactant is preferred.
• the carbon atom number of 3 or more POA chain in the surfactant s 3, polyoxy tetramethylolmethane Len (hereinafter, the POT, U) and Z or a POP chain is preferred.
• a nonionic surfactant represented by the following formula s 31 or s 32 is preferable.
• gl is 0 or an integer from 1 to 200
• t is 2 to: an integer of L00
• g2 is 0 or an integer of 1 to 200. If gl is 0, g2 is an integer greater than or equal to 2, and if g2 is 0, gl is an integer greater than or equal to 2.
• the CHO unit is CH (CH) CH—
• the POA chain is blocky.
• Specific examples of the surfactant s 3 include the following compounds.
• Surfactant s 4 Roh represented by the following formula s 41 - On surfactant is preferred.
• R 17 , R 18 and R 19 each independently represent a monovalent hydrocarbon group.
• a surfactant having an amine oxide (N ⁇ 0) is treated as a nonionic surfactant.
• Surfactant s 4 may be used in combination singly or two or more.
• Surfactant s 4 Roh represented by the following formula s 42 - On surfactant is preferable from the viewpoint of dispersion stability of the copolymer ⁇ .
• R 2G is a phenyl group or an alkenyl group (the number of carbon atoms) to which an alkyl group having 6 to 22 carbon atoms, an alkyl group having 6 to 22 carbon atoms, or an alkyl group (6 to 22 carbon atoms) is bonded.
• 6-22 represents a bonded phenyl group, a fluoroalkyl group having 6 to 13 carbon atoms, an alkyl group having 8 to 22 carbon atoms, an alkyl group having 8 to 22 carbon atoms, or a carbon atom number of 4 to 9 polyfluoroalkyl groups are preferred!
• the substituted phenol group in surfactant s 5 is more preferably a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group, preferably a phenyl group substituted with a monovalent hydrocarbon group. .
• Surfactant s 5 includes polyoxyethylene mono (alkylphenol) ether condensate, polyoxyethylene mono (alkylphenol) ether condensate, polyoxyethylene mono (alkylphenol) ether, polyoxyethylene mono (alkylphenol) ether Preference is given to oxyethylene mono (alkyl ether) ether or polyoxyethylene mono [(alkyl) (styryl) phenol] ether.
• polyoxyethylene mono (substituted phenol) ether condensates or polyoxyethylene mono (substituted phenol) ethers include formaldehyde condensates of polyoxyethylene mono (norphenol) ethers, polyoxyethylene Ethylene mono (norphenyl) ether, polyoxyethylene mono (octylphenol) ether, polyoxyethylene And mono (oleylphenol) ether, polyoxyethylene mono [(nonyl) (styryl) phenol] ether, polyoxyethylenemono [(oleyl) (styryl) phenol] ether, and the like.
• the polyol in the surfactant s 6, represents glycerin, sorbitan, sorbit, Porigurise phosphorus, polyethylene glycol, polyoxyethylene glyceryl ether, Poriokishechi Ren sorbitan ether, polyoxyethylene sorbit ether.
• Surfactant s 6 includes: 1: 1 (molar ratio) ester of octadecanoic acid and polyethylene glycol, 1: 4 (molar ratio) ester of ether of sorbite and polyethylene glycol and oleic acid, and polyoxyethylene glycol 1: 1 (molar ratio) ester of ether and octadecanoic acid with sorbitan, 1: 1 (molar ratio) ester of ether and oleic acid of polyethylene glycol and sorbitan, 1: 1 of dodecanoic acid and sorbitan (Molar ratio) ester, 1: 1 or 2: 1 (molar ratio) ester of oleic acid and decaglycerin, and 1: 1 or 2: 1 (molar ratio) ester of octadecanoic acid and decaglycerin.
• Te Contact ⁇ the present invention when the surfactant includes a cationic Surfactant s 7 is substituted ⁇ Nmo - is preferable to use a ⁇ beam salt form of a cationic surfactant.
• Substituted ammonium salt type cationic surfactants include those in which one or more of the hydrogen atoms bonded to the nitrogen atom are substituted with an alkyl group, an alkyl group or a POA chain having a terminal hydroxyl group.
• compound ⁇ beam salt represented by the preferred instrument following formula s 71 is more preferable.
• R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a POA chain having a hydroxyl group at the end. There, the four R 21 may be the same or different, four R 21 are not hydrogen atom at the same time. Shows strawberry counter ion.
• R 21 is preferably a long-chain alkyl group having 6 to 22 carbon atoms, a long-chain alkenyl group having 6 to 22 carbon atoms, or a fluoroalkyl group having 1 to 9 carbon atoms.
• R 21 is an alkyl group other than a long-chain alkyl group, a methyl group or an ethyl group is preferred.
• R 21 is a PO A group, a POE group is preferred.
• X— is preferably chlorine ion, ethyl sulfate ion or acetate ion.
• the surfactant when the surfactant includes the amphoteric surfactant s 8 , the amphoteric surfactant in the form of alanine, imidazolium betaine, amide betaine or betaine acetate is used. Is preferred.
• R 21 preferably contains a long-chain alkyl group having 6 to 22 carbon atoms, a long-chain alkyl group having 6 to 22 carbon atoms, or a fluoroalkyl group having 1 to 9 carbon atoms.
• amphoteric surfactant s 8 include dodecyl betaine, octadecyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolium betaine, dodecyl dimethylamino acetate betaine, fatty acid amidopropyldimethylamino acetate betaine and the like. Can be mentioned.
• the surfactant contains a ionic surfactant, for example, a carboxylic acid-containing surfactant, a phosphoric acid-containing surfactant, a sulfonic acid-containing surfactant, Examples include fatty acid salts.
• a ionic surfactant for example, a carboxylic acid-containing surfactant, a phosphoric acid-containing surfactant, a sulfonic acid-containing surfactant.
• examples include fatty acid salts.
• the surfactant (III) a block copolymer, a random copolymer or a hydrophilic monomer, a hydrocarbon hydrophobic monomer, and a Z or fluorine hydrophobic monomer may be used. It may be a polymer surfactant (s 9 ) made of a hydrophobic modified product of a hydrophilic copolymer.
• the surfactant (s 9 ) include block or random copolymers of polyethylene glycol (meth) acrylate and long chain alkyl acrylate, polyethylene glycol ( Block or random copolymer of (meth) acrylate and fluoro (meth) acrylate, block or random copolymer of butyl acetate and long-chain alkyl butyl ether, block of butyl acetate and long-chain alkyl butyl ester or Random copolymer, polymer of styrene and maleic anhydride, condensate of polybutyl alcohol and stearic acid, condensate of polybutyl alcohol and stearyl mercaptan, condensate of polyallylamine and stearic acid, polyethyleneimine And condensates of thiol and stearyl alcohol, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose and the like.
• the surfactant (s 9 ) includes Kuraray's MP polymer (Product No .: MP-103, MP-203), Elphatchem's SMA resin, Shin-Etsu Chemical's Metros, Nippon Shokubai's Epomin RP, Seimi For example, Surflon (product number: S-381, S-393) manufactured by Chemical Corporation.
• a block copolymer or a random copolymer of a lipophilic monomer and a fluorine-based monomer (its (Polyfluoroalkyl modified product)
• a high molecular weight surfactant can also be used. Specific examples include a copolymer of alkyl acrylate and fluoro (meth) acrylate, a copolymer of alkyl vinyl ether and fluoroalkyl butyl ether, and the like. No .: S-383, SC-100 series).
• surfactants (el) and Z or surfactant (e2), and surfactant (III), which is also effective with surfactant (e3) are used in total for the polymer.
• a stable aqueous dispersion can be obtained by using a small amount of 5% by mass or less. In addition, it exhibits excellent water repellency and water repellency. Particularly preferably, the content is 4% by mass or less.
• Surfactant (el) At least one of polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkyl polyether, and polyoxyalkylene monopolyfluoroalkyl ether. That is, the surfactant 3 1 .
• Surfactant (e2) A nonionic surfactant comprising a compound having at least one carbon-carbon triple bond and at least one hydroxyl group in the molecule. That is, the surfactant ⁇ Surfactant (e3): Cationic surfactant. In particular compounds of the formula s 71.
• the liquid repellent composition of the present invention may contain an additive (IV)! / ⁇ .
• Additive (IV) is a copolymer
• Addition to an aqueous dispersion containing (I) and copolymer ( ⁇ ) has the effect of reducing the dynamic surface tension of the aqueous dispersion.
• the temperature at which the weight decay of additive (IV) in thermogravimetry is 30% by weight is 250 ° C or less.
• the dynamic surface tension is the surface tension of the moving gas-liquid interface, and is measured by a method called the maximum bubble pressure method or the public pressure differential pressure method.
• Journal of Chemica 1 Society, 121, p858 (1922), Journal of Colloid and Interface Science, 166, p6 (1994) and other documents have shown their principles, measurement methods, and examples, and dedicated measurement devices are also available. It is commercially available.
• thermogravimetric measurement it can be measured using a commercially available thermogravimetric measuring apparatus (TGG-DTA2000S manufactured by Bruker AXS, PyrislTGA manufactured by Perkin Elma Co., Ltd., etc.). Weigh about 10 mg in an aluminum sample cup, raise the temperature from room temperature to 400 ° C at a rate of 10.0 ° CZ min, and check the change in weight!
• TGG-DTA2000S manufactured by Bruker AXS, PyrislTGA manufactured by Perkin Elma Co., Ltd., etc.
• the additive (IV) has the effect of lowering the dynamic surface tension when added to the aqueous dispersion containing the copolymer (I) and the copolymer ( ⁇ ).
• the penetration and wettability of the composition into the substrate can be improved, and excellent water and oil repellency and durability can be imparted.
• the adhesion rate during processing is improved and a particularly excellent effect is obtained.
• the use of the additive (IV) is preferably 1% by mass or less with respect to the aqueous dispersion, and the dynamic surface tension is preferably lowered by 5 mNZm or more.
• the additive (IV) is characterized by high volatility because its weight decay is 30% by weight at 250 ° C or below.
• the water-dispersed composition of the liquid repellent composition When the water-dispersed composition of the liquid repellent composition is applied to the substrate by various methods such as coating, dipping, spraying, etc., and heated and dried under heating conditions of 40 ° C or higher, it remains on the substrate surface. This makes it easy to develop liquid repellency.
• the additive (IV) is preferably at least one hydrophilic group which may be a water-soluble solvent (for example, a hydroxy compound, for example, an alcohol or ether such as 2-propanol.
• a water-soluble solvent for example, a hydroxy compound, for example, an alcohol or ether such as 2-propanol.
• a radical polymerization initiator for initiation of the polymerization reaction, heat, light, radiation, a radical polymerization initiator, an ionic polymerization initiator, or the like is preferably used.
• general-purpose initiators such as azo polymerization initiators, peroxide polymerization initiators, redox initiators and the like, which are preferably water-soluble or oil-soluble radical polymerization initiators, can be used depending on the polymerization temperature.
• a salt of an azo compound is more preferable, particularly when polymerization is carried out in a medium using water where an azo compound is preferable.
• the polymerization temperature is preferably 20 to 150 ° C! /.
• a molecular weight modifier may be used.
• aromatic compounds or mercabtans are preferable, and alkyl mercabtans are particularly preferable.
• Ph represents a phenyl group. And the like are preferred.
• the liquid repellent composition of the present invention includes a penetrating agent, an antifoaming agent, a water absorbing agent, an antistatic agent, an antifungal agent, a texture adjusting agent, a film-forming aid, polyacrylamide and polybulal alcohol, Water-soluble polymers, thermosetting agents such as melamine and urethane resins, isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid dihydrazide, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide) ), 1, 1, 1 ', 1,, 1 tetramethyl Various additives such as epoxy curing agents such as 4,4,1 (methylene-di-para-phenylene) disemicarbazide and spiroglycol, and compounds effective as stabilizers for synthetic resins and fibers may be added. If necessary, use a catalyst in combination with the purpose of promoting thermosetting
• additives can be more effective by adjusting the addition amount, addition method, treatment conditions, etc. according to the characteristics of the substrate.
• fabric treatment it is common to use melamine rosin and a crosslinking catalyst for the purpose of improving the durability of performance, but the amount of addition varies depending on the type of fabric.
• the amount of catalyst applied to the polyester fabric is 1Z20 to LZ5 of nylon fiber.
• the liquid repellent composition of the present invention can be applied to an object to be treated by a known method.
• the liquid repellent composition is dispersed and diluted in an organic solvent or water, adhered to the surface of the object to be treated by dip coating, spray coating, foam coating or the like, and then dried.
• a processing method based on the Exhaust method can be adopted in which the pH is adjusted to about 7 or less, the treatment liquid is attached to the object to be treated, and after heat treatment, it is washed and dehydrated.
• concentration of the fluorine-containing polymer is 0.05 to 10 mass 0/0 in the processing solution.
• the concentration of the fluoropolymer in the treatment liquid is preferably 0.1 to 5% by mass. If by the Exaust method, the concentration of the fluoropolymer in the treatment solution may be between 0.05 to 10 weight 0/0.
• Articles having a liquid repellent film formed using the liquid repellent composition of the present invention include fibers, nonwoven fabrics, resin, paper made of natural fibers, synthetic fibers or blended fibers thereof that are not particularly limited. Leather, metal, stone, concrete, gypsum, glass and other inorganic materials.
• the film is flexible, the texture of the fiber product becomes flexible and high quality water / oil repellency can be imparted to the article.
• it has excellent surface adhesion and can impart water and oil repellency even at low temperature curing.
• it is possible to stably maintain the initial performance with little degradation in performance due to friction or washing.
• excellent size, water repellency and Oil resistance can be imparted to paper.
• a water / oil repellent film having good adhesion to the base material and excellent film forming property can be formed.
• T melting point
• T glass transition point of homopolymer
• FMA. alkyl metatalylate
• VMA surfactant polyoxyethylene glycol ether
• PEO 25 surfactant polyoxyethylene glycol ether
• STMAC stearyltrimethylammonium chloride
• DPG dipropylene glycol
• the obtained mixed solution was treated at 40 MPa using a high-pressure emulsifier (manufactured by APV Lanier Co., Ltd., Minilab) while maintaining the temperature at 60 ° C. to obtain an emulsion.
• a high-pressure emulsifier manufactured by APV Lanier Co., Ltd., Minilab
• V601 dimethyl 2, 2'-azobis (2-methylpropionate)
• VCM salted bull monomer
• a polymerization reaction was carried out in the same manner as in Production Example 1 except that the composition shown in Table 1 was obtained, and an emulsion was obtained. However, monomers other than VCM were charged before emulsification with a high-pressure emulsifier and mixed with a homomixer.
• a polymerization reaction was performed in the same manner as in Production Example 1 except that the composition shown in Table 1 was used, and an emulsion was obtained. However, monomers other than VCM were charged before emulsification with a high-pressure emulsifier, and mixed with a homomixer.
• STA Stearyl Atarylate
• DAAM Diacetone acrylamide
• GMA Glycidylmetatalylate
• PEO-30 Polyoxyethylene glycol ether (Carbohydrate with about 26 mol of ethylene oxide)
• EPO-40 Ethylene oxide propylene oxide polymer (40% ethylene oxide included)
• VA-061A 2, 2, —Azobis [2— (2-Imidazoline—2-yl) propane] acetate
• H OCOC (CH) CH
• PE350 polyethylene glycol methacrylate
• a polymerization reaction was carried out in the same manner as in Production Example 10 except that the copolymer of Production Example 4 was used as the copolymer (I) to obtain an emulsion having a solid content concentration of 34.8% by mass.
• a polymerization reaction was carried out in the same manner as in Production Example 10 except that the copolymer of Production Example 5 was used as copolymer (I) to obtain an emulsion having a solid content concentration of 34.8% by mass.
• copolymer (I) In a stainless steel autoclave, the copolymer produced in Production Example 5 is used as copolymer (I), and 409.4 g of an aqueous dispersion of the copolymer (I) (solid content concentration: 34.2% by mass), and The copolymer ( ⁇ ), 19.9 g of FMA, 7.7 g of CHMA, and 8.4 g of GMA were charged. Further, 0.33 g of StSH, 3.15 g of DPG, and 52.2 g of water were prepared and adjusted so that the total solid content was 35 mass%. The mixture was stirred at 60 ° C. for 1 hour, then cooled, 0.04 g of V-59 was added, and after substitution with nitrogen, VCM was added with 7.
• the polymerization reaction was carried out in the same manner as in Production Example 3 except that 5.78 g of PEO-30 and 0.666 g of STMAC were used in place of PEO-25 as surfactants, and an emulsion having a solid content of 34.8 mass% was obtained. I got.
• a polymerization reaction was carried out in the same manner as in Production Example 10 except that the copolymer produced in Production Example 19 was used as copolymer (I) to obtain an emulsion having a solid content concentration of 35.2% by mass.
• the copolymer produced in Production Example 19 is referred to as Copolymer (I), and instead of 12.5 g of FMA, which is the copolymer (II) in Production Example 10, 12.2 g of FMA and 0.3 g of PFM3 are used.
• the polymerization reaction was carried out in the same manner as in Production Example 10 to obtain an emulsion having a solid content concentration of 35.1% by mass.
• Examples 1 to 5 and Examples 22 to 24 are examples in which the copolymer (I) and the copolymer ( ⁇ ) were mixed as separate particles, and Examples 6 to 13, 20, 21, and 21 were This is an example in which the copolymer (I) and the copolymer (II) are used as a core-shell type.
• Example 14 is an example in which core-shell type particles and a copolymer ( ⁇ ) were mixed.
• Examples 17 and 18 are comparative examples using only the copolymer (I)
• Examples 19 and 20 are comparative examples using only the copolymer ( ⁇ ).
• copolymer ⁇ copolymer ( ⁇ ) is expressed as [mass ratio of copolymer ⁇
• the numbers in parentheses in Tables 4 and 5 represent the solid content ratio when mixing.
• ADH was added to the test solution in an aqueous solution of 0.02 g.
• Other additives were prepared so as to have the concentrations in the table.
• M-3 Sumitex Resin M-3
• ACX Smitex Saccelarator ACX 0.5% by mass, respectively.
• Each treatment bath was prepared so as to be 0.5 mass% of M-3 and 0.05 mass% of ACX.
• the abbreviations in the table indicate the following, and the numbers in parentheses indicate the solid content ratio after mixing.
• Surfynol 104-PG50 manufactured by Air Products Japan Co., Ltd., hereinafter referred to as AGE
• AGE Surfynol 104-PG50
• dipropylene glycol so that the mass% in the table relative to the treatment bath was obtained.
• Surfynol 440 manufactured by Air Products Japan Co., Ltd., hereinafter referred to as “A GE-4”
• PEO-30 were added as a 5 mass% aqueous solution so that the mass% in the table was obtained.
• TP-10 Mei forcenate TP-10Z made by Meisei Chemical Co., Ltd.
• NBP Mei force Nate NBP— 211Z made by Meisei Chemical Co., Ltd.
• ADH Adipic acid dihydrazide
• Example 1 Using the test solution obtained in 24, a dyed nylon cloth or a polyester cloth was dipped and squeezed so that the wet pick-up would be 70% by mass and 60% by mass, respectively. This was dried at 110 ° C for 90 seconds, and then dried at 170 ° C for 60 seconds to obtain test cloth A. [0103] [Evaluation method of water repellency]
• Test Cloth A The water repellency of Test Cloth A was evaluated by the JIS-L1092 spray test (however, the water volume of the spray was 0.25 liter or 1 liter. The water temperature was 27 ° C). The water repellency rating is used. A water repellency rating with + (-) indicates that each property is slightly good (bad).
• Washing durability of test cloth A is determined by repeating washing 5 times (HL-5) 16 times (nylon cloth) or HL-5 40 times (polyester cloth) according to JIS-L0217 Attached Table 103. The water repellency was evaluated after drying at 90 ° C for 15 minutes.
• the rain test for test cloth A is evaluated according to the method described in the JIS-L 1092 (C) method (Bundesman test) under conditions where the rainfall is lOOccZ minutes, the rain water temperature is 20 ° C, and the rain time is 10 minutes. And expressed in 5 grades from 1 to 5.
• the washing durability was evaluated by repeating washing in the same manner as above and then pressing at 130 ° C for 15 seconds. D KUSUN AF-43T was used as the press. The larger the score, the better the water repellency. + (-) Indicates that each property is slightly better (bad).
• the aqueous dispersions obtained in Production Examples 22 to 26 were prepared according to Table 9 so that the solid content concentration was 0.6% by mass for PET (polyethylene terephthalate) and 1.0% by mass for cotton.
• M-3 ZACX was prepared so that the solid content concentration in the working fluid was 0.3% by mass, respectively.
• Examples 25 to 28 are examples in which the copolymer (I) and the copolymer ( ⁇ ) are used as separate particles, and Example 29 is a unit in which the structural units (a), (b) and ( This is a comparative example using a copolymer containing c).
• Table 9 shows that the structural unit (a) and the copolymer of structural unit (b) (I) The mass ratio with respect to) is indicated as [ & ⁇ ] and [].
• the mass ratio of the structural unit (a) and the structural unit (c) forming the copolymer ( ⁇ ) to the copolymer ( ⁇ ) is expressed as [a] and [c
• the copolymer ⁇ copolymer ( ⁇ ) is [mass ratio of copolymer ⁇ ] ⁇ [mass ratio of copolymer ( ⁇ )].
• the mass ratio of each structural unit in the entire copolymer (copolymer (I) + copolymer ( ⁇ )) is shown as [a], [b], [c], and [d].
• the numbers in parentheses in Table 9 represent the solid content ratio when mixing.
• Table 10 shows the results of evaluation of water repellency according to the evaluation method described above after drying overnight in a room adjusted to room temperature 25 ° C and humidity 55%.
• each processed cloth was repeatedly washed in the same manner as the above-mentioned washing durability, and then dried at 90 ° C for 15 minutes to prepare a test cloth.
• the test cloth was subjected to elemental analysis on the cloth surface by X-ray photoelectron spectroscopy. Table 11 shows the results for the concentration of elemental fluorine.
• Example 25 to 28 sufficient liquid repellency and high durability were obtained even though the total proportion of each structural unit contained in the entire copolymer was the same as in Example 29. (Table 10). Thus, when the copolymer (I) and the copolymer ( ⁇ ) were mixed and used as separate particles, sufficient liquid repellency and high durability could be confirmed. Similarly, in Examples 1 to 5 and 22 to 24, in which the copolymer (I) and the copolymer ( ⁇ ) were mixed and used as separate particles, high liquid repellency and durability were obtained. . In addition, when the copolymer (I) and the copolymer ( ⁇ ⁇ ) are used in a core-shell type (Examples 6 to 13, 15, 16, 21), sufficient liquid repellency and high durability can be obtained. It was.
• liquid repellent film formed by the liquid repellent composition of the present invention has little surface change due to friction and high durability (Table 11).
• Fig. 1 shows the results of thermogravimetry for each additive used in the examples.
• Bull force I. TG-DTA2000S manufactured by AXS was used.
• ⁇ 5.2 mm height 5.1 mm deep Weighed 10 mg of the additive to be measured and measured the change in weight when the room temperature was raised to 400 ° C at 10 ° C / min.
• Figure 2 shows the change in dynamic surface tension with and without additives, taking Example 6 as an example.
• the measurement was performed using FACE BP-D3 manufactured by Kyowa Interface Science.
• the liquid repellent composition of the present invention exhibits practically necessary functions such as sufficient water / oil repellency and durability. This is estimated according to the synergistic effect of immobilization of promotion and the R f group on the surface orientation of the R f group.
• Water and oil repellents (liquid repellents) based on this principle can form a coating film at a lower temperature than conventional water and oil repellents, and the resulting coating film is flexible and tough and has excellent adhesion to the substrate. . Therefore, it is possible to impart water and oil repellency to the article without lowering the quality such as hardening of the texture and embrittlement of the film, which were the conventional problems. Further, the obtained article can impart sufficient water and oil repellency even when processed at a lower temperature than conventional. In addition, there is little degradation in performance due to wear or washing. In addition, the adhesion during laminating and coating is much improved over conventional water and oil repellents.
• the copolymer in the present invention has good solubility in a fluorine-based solvent having a small influence on the ozone layer, such as an alcohol solvent, a weak solvent, and a hydrated fluorocarbon, it is problematic in terms of environment and safety. Little! /, Solvent can be used as solvent.
• the liquid repellent composition of the present invention includes sportswear, coats, blousons, clothing articles such as work clothes or uniforms, and textile products such as bags and industrial materials, non-woven fabrics, leather products, stone materials, Used for water and oil repellent treatment of concrete building materials. It is also used as a coating agent for filter materials, surface protective agents, electronic coating agents, and antifouling coating agents used in the presence of organic solvent liquids or vapors thereof. It is also used in applications that impart water and oil repellency by mixing and molding with Sarakiko, polypropylene, nylon, etc. It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2006-092929 filed on March 30, 2005 are hereby incorporated herein by reference. As it is incorporated.

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